CA1271616A - Process for production of silane - Google Patents
Process for production of silaneInfo
- Publication number
- CA1271616A CA1271616A CA000482693A CA482693A CA1271616A CA 1271616 A CA1271616 A CA 1271616A CA 000482693 A CA000482693 A CA 000482693A CA 482693 A CA482693 A CA 482693A CA 1271616 A CA1271616 A CA 1271616A
- Authority
- CA
- Canada
- Prior art keywords
- producing silane
- silane
- silane according
- silica
- recovered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
Abstract:
Process for production of silane Disclosed is a process for producing silane, which comprises mixing silica powder recovered from geothermal hot water with metallic magnesium powder, reducing by heating the resultant powdery mixture to convert it to magnesium silicide and then reacting an ammonium halide in liquid ammonia or an inorganic acid with said magnesium silicide.
According to the process of the present invention, there can be obtained such effects as (1) high yield of silane, (2) simple production step which enables reduction in production cost and (3) contribution to effective utilization of geothermal water, and its industrial value is great.
Process for production of silane Disclosed is a process for producing silane, which comprises mixing silica powder recovered from geothermal hot water with metallic magnesium powder, reducing by heating the resultant powdery mixture to convert it to magnesium silicide and then reacting an ammonium halide in liquid ammonia or an inorganic acid with said magnesium silicide.
According to the process of the present invention, there can be obtained such effects as (1) high yield of silane, (2) simple production step which enables reduction in production cost and (3) contribution to effective utilization of geothermal water, and its industrial value is great.
Description
- ~7163L6 Process for ~roduction of silane BACKGROUND OF THE INVENTION
This invention relates to a process for producing silane, more particularly to a process for producing silane at low cost and high yield by use of silica recovered from geothermal hot water as the silica source.
Recently, the demand for polycrystalline silicon is increasing as the material for solar battery and semiconductor. Such a polycrystalline silicon is produced industrially according to, for example, the pyrolysis method in which monosilane is delivered into a pyroIysis furnace to be brought into contact with the surface of silicon core wire heated by current passage at 800 to 1000 C to decompose and precipitate monosilane ; 15 thereat (rod-shaped product) or the fluidized method in which monosilane is delivered into a fluidized-bed reactor filled with silicon particles of predetermined particle sizes to be pyrolyzed therein (powdery product).
Accordingly, in production of polycrystalline silicon, it is necessary to use silane as the starting material.
At present, as the process for production of silane, are :~
~LX7~
widely known (1) the so-called Siemens process wherein heating reduction treatment is applied on a mixture of silica and a carbon material in an arc furnace to produce metallic silicon, which metallic silicon i5 then halogenated into, for example, dichlorosilane, which dichlorosilane is subjected to disproportionation to produce silane and (2) the so called Stock process wherein silica is allowed to react with metallic magnesium to form magnesium silicide, which magnesium silicide is then reacted with an ammonium halide in liquid ammonia or an inorganic acid such as hydrochloric acid to produce silane.
The process ~1), while having the advantage o producing a high purity silane, involves on the other hand the problem of including a diversity of complicated steps to make the production cost higher. In contrast, the process (2) poses a problem in low yield of silane (about 25 ~).
Thus, in representative processes for production of silane, th state of the art has, not necessarily been satisfactory with respect to production cost and yield.
SUMMARY OF THE I'.~VENTION
An object of the present invention is to provide a process which can produce silane at high yield and low cost.
The present inventor, in order to accomplish the above object, has made various investigations about the process : (2) and found that the yield of silane becomes higher as compared with that of the prior art by use of silica contained in geothermal hot water in place of silica or quartz po~der conventionally used as the silicon source ~7~
for magnesium silicide, to accomplish the present invention.
More speciically, the process for producing silane of the present invention comprises mixing silica powder recovered from geothermal hot water with metallic magnesium powder, reducing by heating the resultant powdery mixture to convert it to magnesium silicide and then reacting an ammonium halide in li~uid ammonia or an inorganic acid with said magnesium silicide.
DESCRIPTION OF PREFERRED EMBODIMENTS
The silicon source in the present invention is the silica recovered from geothermal hot water. The recovered silica can be obtained as follows. That is, geothermal hot water having a temperature oE 200 C or higher at the bowels of the earth and having a temperature of about 80 to 100 oC when sprung out, is left to stand stationarily under room temperature. It is preferred to use geothermal hot water having a silica content of 200 to 1000 ppm. The time for stationary standing may be about
This invention relates to a process for producing silane, more particularly to a process for producing silane at low cost and high yield by use of silica recovered from geothermal hot water as the silica source.
Recently, the demand for polycrystalline silicon is increasing as the material for solar battery and semiconductor. Such a polycrystalline silicon is produced industrially according to, for example, the pyrolysis method in which monosilane is delivered into a pyroIysis furnace to be brought into contact with the surface of silicon core wire heated by current passage at 800 to 1000 C to decompose and precipitate monosilane ; 15 thereat (rod-shaped product) or the fluidized method in which monosilane is delivered into a fluidized-bed reactor filled with silicon particles of predetermined particle sizes to be pyrolyzed therein (powdery product).
Accordingly, in production of polycrystalline silicon, it is necessary to use silane as the starting material.
At present, as the process for production of silane, are :~
~LX7~
widely known (1) the so-called Siemens process wherein heating reduction treatment is applied on a mixture of silica and a carbon material in an arc furnace to produce metallic silicon, which metallic silicon i5 then halogenated into, for example, dichlorosilane, which dichlorosilane is subjected to disproportionation to produce silane and (2) the so called Stock process wherein silica is allowed to react with metallic magnesium to form magnesium silicide, which magnesium silicide is then reacted with an ammonium halide in liquid ammonia or an inorganic acid such as hydrochloric acid to produce silane.
The process ~1), while having the advantage o producing a high purity silane, involves on the other hand the problem of including a diversity of complicated steps to make the production cost higher. In contrast, the process (2) poses a problem in low yield of silane (about 25 ~).
Thus, in representative processes for production of silane, th state of the art has, not necessarily been satisfactory with respect to production cost and yield.
SUMMARY OF THE I'.~VENTION
An object of the present invention is to provide a process which can produce silane at high yield and low cost.
The present inventor, in order to accomplish the above object, has made various investigations about the process : (2) and found that the yield of silane becomes higher as compared with that of the prior art by use of silica contained in geothermal hot water in place of silica or quartz po~der conventionally used as the silicon source ~7~
for magnesium silicide, to accomplish the present invention.
More speciically, the process for producing silane of the present invention comprises mixing silica powder recovered from geothermal hot water with metallic magnesium powder, reducing by heating the resultant powdery mixture to convert it to magnesium silicide and then reacting an ammonium halide in li~uid ammonia or an inorganic acid with said magnesium silicide.
DESCRIPTION OF PREFERRED EMBODIMENTS
The silicon source in the present invention is the silica recovered from geothermal hot water. The recovered silica can be obtained as follows. That is, geothermal hot water having a temperature oE 200 C or higher at the bowels of the earth and having a temperature of about 80 to 100 oC when sprung out, is left to stand stationarily under room temperature. It is preferred to use geothermal hot water having a silica content of 200 to 1000 ppm. The time for stationary standing may be about
2~ one week. Silica particles exist under colloidal state.
Then, the colloidal solution is subjected to ultra-filtration to concentrate the solid to about 20 ~, and the concentrate is dried by, for example, spray drying to become powdered at the same time. The particle size and the water content of the recovered silica depends on the conditions employed in these treatments, but it is generally preferred to manage a particle size to 1 to 50 ~m and the water content to 1 to 50 wt. %, preferably 10 to 20 ~m and 4 to 20 ~m, respectively, in the process of the present invention.
The recovered silica obtained by th~ above method and metallic maynesium powder are mixed together. Magnesium employed should desirably as pure as possible. The 1~7~
amount of metallic magnesium mixed is made excessive by 10 to 20 % by weight than the calculated amount corresponding to magnesium silicide (~g2Si).
Subsequently, the powdery mixture is placed in a vessel containing no carbon (e.g. a boat made of iron), and the whole vessel is heated in a reductive atmosphere such as hydrogen gas stream. The heating temperature is generally 400 to 800 C, preferably 500 to 600 C.
It is also possible to form once the powdery mixture into pellets by a disc molding machine prior to the heating reducing treatment.
Deep violet magnesium silicide is obtained. The magnesium silicide is placed in a gas generator such as Kipp's gas generator, and an ammonium halide in liquid ammonia or an inorganic acid such as hydrochloric acid is added dropwise thereinto, whereby silane gas comprising a mixture of SiH4, Si2H6, Si3H8 will be generated with emission of white fume.
Example Geothermal water of about 100 C and having a silica content of 500 ppm sprung out from a geothermal well was left to stand at room temperature for one week. The colloidal solution was filtered through an ult~a-~ k f filtration membrane (trade name: Labomodule, produaad by ~` 25 Asahi Kasei Kogyo K.K.) and silica components were recovered by spray drying. The silica recovered was found to have a primary particle size of 100 to 200 A, with a composition o~ SiO2 96 %, ~12O3 0.5 ~, Fe2O3 1.5 % r Na2O 1 % and CaO 1%.
.
One part by weight of the recovered silica was mixed with L~
2 parts by weight of matallic magnesium powder passed through the lO0 mesh Tyler screen, and the resultant powdery mixture was molded in a stainless steel mold under a pressure of 600 Kg/cm2. A tablet with a diameter of 30 mm and a thickness of about 6 mm was obtained.
The tablet thus obtained was placed in a crucible made of iron equipped with a lid and heated to 500 C in an electric furnace under stream of hydrogen. A deep violet porous spongy product was obtained.
The spongy product was cooled, placed in Kipp's gas generator and 1 N hydrochloric acid was added dropwise thereto. Silane gas was generated with emission of white fume. The amount of the silane gas generated was found to correspond to 66 % of the silicon amount of the recovered silica.
For the purpose of comparison, magnesium silicide was produced in the same manner as described above except for using a quartz component with an average particle size of 5 ~m. The amount of the silane gas generated from this material was found to correspond to 14 % of the silicon amount of the starting material.
As can clearly be seen from the above description, according to the process of the present invention, there can be obtained such effects as tl) high yield of silane, ~5 (2) simple production step which enables reduction in production cost and (3) contribution to effective utilization of geothermal water, and its industrial value is great.
Then, the colloidal solution is subjected to ultra-filtration to concentrate the solid to about 20 ~, and the concentrate is dried by, for example, spray drying to become powdered at the same time. The particle size and the water content of the recovered silica depends on the conditions employed in these treatments, but it is generally preferred to manage a particle size to 1 to 50 ~m and the water content to 1 to 50 wt. %, preferably 10 to 20 ~m and 4 to 20 ~m, respectively, in the process of the present invention.
The recovered silica obtained by th~ above method and metallic maynesium powder are mixed together. Magnesium employed should desirably as pure as possible. The 1~7~
amount of metallic magnesium mixed is made excessive by 10 to 20 % by weight than the calculated amount corresponding to magnesium silicide (~g2Si).
Subsequently, the powdery mixture is placed in a vessel containing no carbon (e.g. a boat made of iron), and the whole vessel is heated in a reductive atmosphere such as hydrogen gas stream. The heating temperature is generally 400 to 800 C, preferably 500 to 600 C.
It is also possible to form once the powdery mixture into pellets by a disc molding machine prior to the heating reducing treatment.
Deep violet magnesium silicide is obtained. The magnesium silicide is placed in a gas generator such as Kipp's gas generator, and an ammonium halide in liquid ammonia or an inorganic acid such as hydrochloric acid is added dropwise thereinto, whereby silane gas comprising a mixture of SiH4, Si2H6, Si3H8 will be generated with emission of white fume.
Example Geothermal water of about 100 C and having a silica content of 500 ppm sprung out from a geothermal well was left to stand at room temperature for one week. The colloidal solution was filtered through an ult~a-~ k f filtration membrane (trade name: Labomodule, produaad by ~` 25 Asahi Kasei Kogyo K.K.) and silica components were recovered by spray drying. The silica recovered was found to have a primary particle size of 100 to 200 A, with a composition o~ SiO2 96 %, ~12O3 0.5 ~, Fe2O3 1.5 % r Na2O 1 % and CaO 1%.
.
One part by weight of the recovered silica was mixed with L~
2 parts by weight of matallic magnesium powder passed through the lO0 mesh Tyler screen, and the resultant powdery mixture was molded in a stainless steel mold under a pressure of 600 Kg/cm2. A tablet with a diameter of 30 mm and a thickness of about 6 mm was obtained.
The tablet thus obtained was placed in a crucible made of iron equipped with a lid and heated to 500 C in an electric furnace under stream of hydrogen. A deep violet porous spongy product was obtained.
The spongy product was cooled, placed in Kipp's gas generator and 1 N hydrochloric acid was added dropwise thereto. Silane gas was generated with emission of white fume. The amount of the silane gas generated was found to correspond to 66 % of the silicon amount of the recovered silica.
For the purpose of comparison, magnesium silicide was produced in the same manner as described above except for using a quartz component with an average particle size of 5 ~m. The amount of the silane gas generated from this material was found to correspond to 14 % of the silicon amount of the starting material.
As can clearly be seen from the above description, according to the process of the present invention, there can be obtained such effects as tl) high yield of silane, ~5 (2) simple production step which enables reduction in production cost and (3) contribution to effective utilization of geothermal water, and its industrial value is great.
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing silane, which comprises mixing silica powder recovered from geothermal hot water with metallic magnesium powder, reducing by heating the resultant powdery mixture to convert it to magnesium silicide and then reacting an ammonium halide in liquid ammonia or an inorganic acid with said magnesium silicide.
2. The process for producing silane according to Claim 1, wherein said geothermal hot water has a silica content of 200 to 1000 ppm.
3. The process for producing silane according to Claim 1, wherein the amount of said metallic magnesium powder to be mixed is made excessive by 10 to 20 % by weight than the calculated amount corresponding to magnesium silicide.
4. The process for producing silane according to Claim 1, wherein hydrogen gas atmosphere is employed in said reductive atmosphere.
5. The process for producing silane according to Claim 1, wherein said heat treatment is conducted at a temperature of 400 to 800 °C.
6. The process for producing silane according to Claim 5, wherein said heat treatment is conducted at a temperature of 500 to 600 °C.
7. The process for producing silane according to Claim 1, wherein said inorganic acid is hydrochloric acid.
8. The process for producing silane according to Claim 1, wherein said recovered silica is treated to have a particle size of 1 to 50 µm and a water content of 1 to 50 wt. %.
9. The process for producing silane according to Claim 8, wherein said recovered silica is treated to have a particle size of 10 to 20 µm and a water content of 4 to 20 wt. %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59115480A JPS60260419A (en) | 1984-06-07 | 1984-06-07 | Manufacture of silane |
| JP115480/84 | 1984-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1271616A true CA1271616A (en) | 1990-07-17 |
Family
ID=14663562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482693A Expired - Fee Related CA1271616A (en) | 1984-06-07 | 1985-05-29 | Process for production of silane |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4704264A (en) |
| EP (1) | EP0164250B1 (en) |
| JP (1) | JPS60260419A (en) |
| CA (1) | CA1271616A (en) |
| DE (1) | DE3565247D1 (en) |
| NZ (1) | NZ212219A (en) |
| PH (1) | PH20972A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479211A (en) * | 2020-12-17 | 2021-03-12 | 烟台万华电子材料有限公司 | Method for continuously producing disilane |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2927620A1 (en) * | 2008-02-14 | 2009-08-21 | Guillonnet Didier | Producing silane gas by reacting either a diluted acid, hot water or water vapor on magnesium silicide, comprises purification of magnesium silicide in powder form by a cold water bath |
| WO2009121170A1 (en) * | 2008-03-31 | 2009-10-08 | Et-Energy Corp. | Chemical process for generating energy |
| CN102030333B (en) * | 2010-11-29 | 2012-07-25 | 范清春 | Method for industrially preparing silane |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2551571A (en) * | 1949-01-14 | 1951-05-08 | Union Carbide & Carbon Corp | Method of producing silanes |
| DE926096C (en) * | 1952-08-20 | 1955-04-07 | Steiner Walter | Vending machine with rotatable vending fan plate and coin plate arranged above it under a transparent bell with side removal opening |
| FR1257306A (en) * | 1960-04-27 | 1961-03-31 | Method and apparatus for the manufacture of pure monosilane | |
| JPS4214708Y1 (en) * | 1964-03-31 | 1967-08-22 | ||
| JPS4822918B1 (en) * | 1967-10-31 | 1973-07-10 | ||
| JPS4998399A (en) * | 1973-01-27 | 1974-09-18 | ||
| JPS57135717A (en) * | 1981-02-13 | 1982-08-21 | Mitsui Mining & Smelting Co Ltd | Preparation of synthetic zeolite |
| JPS60260499A (en) * | 1984-06-07 | 1985-12-23 | Idemitsu Kosan Co Ltd | Preparation of sic whisker |
-
1984
- 1984-06-07 JP JP59115480A patent/JPS60260419A/en active Granted
-
1985
- 1985-05-27 NZ NZ212219A patent/NZ212219A/en unknown
- 1985-05-29 CA CA000482693A patent/CA1271616A/en not_active Expired - Fee Related
- 1985-05-30 DE DE8585303827T patent/DE3565247D1/en not_active Expired
- 1985-05-30 EP EP85303827A patent/EP0164250B1/en not_active Expired
- 1985-06-04 PH PH32361A patent/PH20972A/en unknown
-
1986
- 1986-07-07 US US06/883,288 patent/US4704264A/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479211A (en) * | 2020-12-17 | 2021-03-12 | 烟台万华电子材料有限公司 | Method for continuously producing disilane |
| CN112479211B (en) * | 2020-12-17 | 2022-10-04 | 烟台万华电子材料有限公司 | Method for continuously producing disilane |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ212219A (en) | 1988-04-29 |
| JPS64326B2 (en) | 1989-01-06 |
| US4704264A (en) | 1987-11-03 |
| JPS60260419A (en) | 1985-12-23 |
| DE3565247D1 (en) | 1988-11-03 |
| EP0164250B1 (en) | 1988-09-28 |
| EP0164250A2 (en) | 1985-12-11 |
| EP0164250A3 (en) | 1986-03-19 |
| PH20972A (en) | 1987-06-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |